Kael krekeler and eduard martz



UNITED STATES PATENT OEErcE.

KARL KREKELER AND EDUARD MARTZ, OF ELBERFELD, GERMANY, ASSIGNORS TO THE FARBENFABRIKEN OF ELBERFELD COMPANY,

OF NEW YORK, N. Y.

BROWN TRISAZO DYE.

SPECIFICATION forming part of Letters Patent No. 603,090, dated April 26, 1898.

Application filed November 23, 1897. Serial No. 659,583. (Specimen) Patented in Germany September 15,1891, No. 66,262 in England December 8. 9 1 1; in France April 28, 1892,110. 221,233 in Italy June so, 1892, XXVI, 32,191, LXIII, 186, and in Austria-Hungary October 3, 1892, No, 1,242 and No. 16,870.

To all whom it may concern:

Be it known that we, KARL KREKELER and EDUARD MARTZ, doctors of philosophy, chemists, (assignors to the FA'BBENFAB'RIKEN on ELBERFELD COMPANY, of New York,) have invented a new and useful Improvement in the Manufacture of Trisazo Dye, (for which the Farbenfabriken, vormals Fr. Bayer & 00., of Elberfeld, Germany, has already obtained Letters Patent in Germany, No. 65,262, dated September 15, 1891; in England, No. 22,641, dated December 28, 1891; in France, No. 221,233, dated April 28, 1892; in Italy, Reg. Gen, Vol. XXVI, No. 32,191, Reg. Att., Vol. LXIII, No. 186', dated June 30, 1892, and in Austria-Hungary, No. 1,2i2 and No. 16,870, dated October 3, 1892 and we hereby declare the following to be a clear and exact description of our invention.

In a simultaneous application, Serial No. 659,582, bearing the same date, we have described a process for producing trisazo dyestufis by combining one molecule of the diazo derivative of a tetra-Z0 compound of the general formula Orthoiixycarbonic acid Paradiamin (tetrazotized) Clves naphthylaminsulfo-acid with one molecule of an orthooxycarbonic acid of the benzene series, such as salicylic acid or cresotinic acid. 0 ur present invention relates to the production of a new class of trisazo coloring-matters by combining one molecule of the said diazo derivatives with one molecule of a metadiamin of the benzene series, such as metaphenylenediamin or metatoluylenediamin, or a monosulfo-acid thereof. The dyestuifs thus produced represent dark powders soluble in water with a color varying from reddish brown to dark brown. They dye unmordanted cotton from reddish-brown to brown shades, which when treated with solutions of chromium and copper salts become more yellowish brown and faster to washing and against the action of light. The

coloring-matters are also capable of dyeing wool.

In carrying out our new process practically we can proceed as follows: 18.4 kilos, by weight, of benzidin are diazotized in the usual manner by means of fourteen kilos, by weight, of sodium nitrite. To the icy-cold diazo solution an icy-cold solution of fourteen kilos,-

by weight, of salicylic acid and seventy kilos, by Weight, of sodium carbonate (Na,OO in four hundred liters of water is added with stirring. When the formation of the intermediate product is finished, a cold solution prepared by dissolving 24.5 kilos, by weight, of the sodium salt of alpha-naphthylaminbeta-monosulfo-acid (1.6) in three hundred liters of Water is added. After about three hours stirring the formation of the intermediate dyestuff is complete. The mixture is subsequently acidulated by means of hydrochloric acid and filtered. The dyestuff acid thus obtained is dissolved in fifteen hundred liters of a 2.5 per cent. soda-lye, then quickly mixed with a solution of eight kilos, by weight, of sodium nitrite, five hundred kilos, by weight, of ice, and one hundred and fifty kilos, by weight, of hydrochloric acid, (20 Baume'.) This mixture is stirred for about twelve hours. The resulting insoluble diazo compound is filtered aud pressed. Subsequently it is mixed with ice and water to a thin paste, which is slowly stirred into an icy-cold solution of 22.4 kilos, by weight, of metatoluylenediamin sulfonate of sodium having the formula NaO -,S on,

H,N NH,

and seventy kilos, by weight, of sodium oarbonate in four h undred liters of water. After stirring this mixture for several hours it is heated to about centigrade, and the fint Salicylio acid Cleves naphthylaminsnlfo-acid (diazotized) metatolnylenediaminsulfoacid Benzidin (te razotized) and represents a dark-brown powder, soluble in water with a reddish-brown color. In concentrated sulfuric acid it dissolves with a blue color, from which solution a reddish-brown flaky precipitate is obtained on the addition of a sufficient quantity of ice. It dies unmordanted cotton reddish-brown shades, which when treated with solutions of chr0- miuin and copper salts become more yellowish brown and faster to Washing and against the action of light. also capable of dyeing wool.

Having now described our invention and in what manner the same is to be performed, what we claim as new, and desire, to scour by Letters Patent, i:-'

1. The process for producing new trisazo dyestuffs by combining one molecule of the diazo derivative of atet'razo body of the general formula Ortho6xycarbonic acid Cleves naphthy1aminsulfo-acid with one molecule of a metadiamin of the benzene series such as metaphenylenediamin, metatoluylenediamin or a sulfo-acid thereof substantially as hereinbefore described.

2. The process for producing a new trisazo dyestuff by combining the diazo derivative of the tetrazo body having the formula Salicylic acid Benzidin (tetrazotized) Oleves naphthylaminsulfo-acid with one molecule of the metatoluylenediamlnmonosulfo-acid having the formula Paradiamin (tetrazotized) orr,

substantially as hereinbefore described.

The coloring-matter is 3. As new articles of manufacture the new trisazo dyestuffs obtainable from the diazo derivative of the tetrazo body of the general formula:

0rthodxycarbonio acid tized)' Oleves naphthylaminsulfo-acid by combination with a metadiamin compound of the benzene series, such as metaphenylenediamin, metatoluylenediamin and sulfo acids thereof, being dark powders soluble in water Paradiamin (tetrazo with a color varying from reddish brown to dark brown, dyeing cotton from reddish brown to dark-brown shades which when treated with solutions of chromium and copg per salts become more yellowish brown and faster to washing and against the action of li ht.

4. As a new article of manufacture the specific dyestuff obtainable from the diazo derivative of the tetrazo body having the formula:

' ,Salicylic acid Benzidin (tetrazotized) Cleves naphthylaminsulfo-acid Benzidin (tetrazotized) centrated sulfuric acid with a blue color from i which solution a reddishbrown precipitate is obtained on the addition of a sufficient quantity of ice, dyeing cotton reddish-brown shades which when treated with solutions of chromium and copper salts. become more yellowish brown and faster to washing and against the action of the light.

In testimony whereof We have signed our names in the presence of two subscribing witnesses.

KARL KREKELER. EDUARD MARTZ.

Witnesses:

R. E. JAHN, OTTO KoNIG. 

